Preparation of a caryophyllene alcohol mixture

ABSTRACT

A process for preparing a mixture of isomers of caryophyllene alcohol and dihydrocaryophyllene alcohol including 10,10-dimethyl-2,6-dimethylene bicyclo[7.2.0]undecan-5-ol by isomerizing caryophyllene oxide or dihydrocaryophyllene oxide using an aluminum isopropylate catalyst in a toluene solvent at temperatures in the range of from about 100° C. up to about 150° C. is described.

BACKGROUND OF THE INVENTION

This invention concerns an improved process of preparing isomers ofcaryophyllene alcohols and dihydro caryophyllene alcohols. Morespecifically, this invention is concerned with preparation of a specificisomer mixture range of caryophyllene alcohols and dihydro caryophyllenealcohols by means of the catalytic isomerization of caryophyllene oxideand dihydro caryophyllene oxide.

Swiss Pat. No. 549,960, issued on Apr. 30, 1974, as well as U.S. Pat.Nos. 4,014,350 (issued on Mar. 29, 1977); 3,840,023 (issued on Oct. 8,1974) and 3,937,228 (issued on Feb. 10, 1976) disclose the organolepticutility of isomers of caryophyllene alcohol produced according to ourinvention in oriental tobacco. The structures of these caryophyllenealcohol isomers are: ##STR1##

It is indicated in said Swiss Pat. No. 549,960 that these materials maybe prepared according to the procedure set forth in Helv. Chim. Acta,51, 494 (1968) Schulte-Elte and Ohloff. In this article it is indicatedthat the dye-sensitized photooxygenation of isocaryophyllene leads toformation of several alcohols having the structures: ##STR2##

The reaction to convert caryophyllene oxide to various isomer mixturesof alcohols is also disclosed in Tetrahedron 27, 635 (1971) andTetrahedron Letters 8 659 (1971) whereby the reaction: ##STR3## iscarried out; in Tetrahedron 27 using an aluminum oxide catalyst and inTetrahedron Letters 8 using a pyridinium bromide/pyridine catalystsystem.

Nothing in the prior art, however, discloses our process for producingthe caryophyllene alcohol isomer mixtures or the dihydro caryophyllenealcohol mixtures of our invention whereby a fast commercially feasiblereaction takes place without the use of any noxious solvents (e.g.,pyridine) and nothing in the prior art discloses the specific reactionproduct mixtures produced according to the process of our invention.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is the GLC profile for the caryophyllene alcohol mixture producedaccording to Example I, fractions 7 and 8.

FIG. 2 is the Mass Spectrum for peak 1 of the caryophyllene alcoholmixture produced according to Example I and contains substantially allcompound having the structure: ##STR4##

FIG. 3 is the NMR spectrum for peak 1 of the caryophyllene alcoholmixture produced according to Example I.

FIG. 4 is the IR spectrum for peak 1 of the caryophyllene alcoholmixture produced according to Example I.

FIG. 5 is the mass spectrum for peak 2 of the caryophyllene alcoholmixture produced according to Example I which caryophyllene alcohol hasone of the structures: ##STR5##

FIG. 6 is the NMR spectrum for peak 2 of the caryophyllene alcoholmixture produced according to Example I having one of the structures:##STR6##

FIG. 7 is the infrared spectrum for peak 2 of the caryophyllene alcoholmixture produced according to Example I having one of the structures:##STR7##

FIG. 8 is the mass spectrum for peak 3 of the caryophyllene alcoholmixture produced according to Example I having one of the structures:##STR8##

FIG. 9 in the NMR spectrum for peak 3 of the caryophyllene alcoholmixture produced according to Example I having one of the structures:##STR9##

FIG. 10 is the infrared spectrum for peak 3 of the caryophyllene alcoholmixture produced according to Example I having one of the structures:##STR10##

FIG. 11 is the GLC profile for the reaction product of Example II,fraction 8.

FIG. 12 is the infrared spectrum for fraction 8 of the reaction productproduced according to Example II.

THE INVENTION

The invention relates to a process for preparing caryophyllene alcoholmixtures from caryophyllene oxide according to the reaction scheme:##STR11## or a dihydro caryophyllene alcohol mixture from dihydrocaryophyllene according to the reaction scheme: ##STR12## using analuminum isopropylate/toluene catalyst system.

The caryophyllene alcohol mixtures and dihydro caryophyllene alcoholmixtures produced according to our invention have musky, orientalsandalwood aroma and flavor characteristics causing them to be useful inraspberry, peach, apricot and blackberry flavors. In addition thecaryophyllene alcohol mixture of our invention has a sweet, woody,peppery aroma with sweet, woody topnotes and slight borneol backgroundcausing it to be extremely useful in the perfume composition field andcausing it to be useful for incorporation into perfumed articles such assoaps and detergents. The structures of the three caryophyllene alcoholisomers produced according to our invention are: ##STR13##

In accordance with the present invention, it has now been found that thenovel mixtures of caryophyllene alcohols and dihydro caryophyllenealcohols of our invention may be prepared from caryophyllene oxide anddihydro caryophyllene oxide by treatment of the caryophyllene oxide ordihydro caryophyllene oxide at elevated temperatures with an aluminumisopropylate/toluene catalyst system.

As will be seen from Table I in Example I, the amounts of isomers of thethree caryophyllene alcohols prepared from caryophyllene oxide havingthe structures: ##STR14## will vary from about 30:65:5 to 8:40:30.

It is preferable that the reaction be carried out at temperaturesbetween 100° C. and 150° C. with reflux temperatures at atmosphericpressure being preferred (e.g. 110°-112° C.). The concentration ofaluminum isopropylate catalyst in the reaction mass may vary from about0.025 molar up to about 0.75 molar with a preferred concentration ofaluminum isopropylate being about 0.04-0.10 molar. The concentration ofcaryophyllene oxide or dihydro caryophyllene oxide in the reaction massmay vary from about 0.25 molar up to about 1.00 molar with a preferredconcentration of caryophyllene oxide or dihydro caryophyllene oxidebeing from 0.40 and 0.50 molar.

The reaction time is dependent on the temperature of reaction to a greatextent. However, it is preferred that a reaction time of from about 1 upto about 5 hours be used in carrying out this reaction. Additional timeof reaction does not improve the yield and a shorter reaction time givesrise to a much lower yield. At temperatures above about 150° C. thecatalyst loses its effectiveness and undesirable side reactions ordegradation of the caryophyllene alcohol or dihydro caryophyllenealcohol reaction product and caryophyllene oxide or dihydrocaryophyllene oxide reactant may occur.

Atmospheric, subatmospheric or above atmospheric pressures can be used,although for reasons of convenience, substantially atmospheric pressuresare preferred.

The caryophyllene alcohols and dihydro caryophyllene alcohols obtainedcan readily be recovered by conventional techniques. Thus, the toluenesolvent employed is removed on a rotary evaporator. The residue is thensubjected to "Rushover" distillation or fractional distillation whichwill yield the desired fractions containing the three caryophyllenealcohol isomers or the several dihydro caryophyllene alcohol isomers inthe desired isomer ratio.

When the caryophyllene alcohol or dihydrocaryophyllene alcohol isomermixture of our invention are used as food flavor adjuvants, the natureof the co-ingredients included with each of the said caryophyllenealcohol or dihydrocaryophyllene alcohol isomer mixture of our inventionin formulating the product composition will also serve to alter, modify,augment or enhance the organoleptic characteristics of the ultimatefoodstuff treated therewith.

As used here in regard to flavors, the terms "alter", "modify" and"augment" in their various forms mean "supplying or imparting flavorcharacter or note to otherwise bland, relatively tasteless substances oraugmenting the existing flavor characteristic where a natural flavor isdeficient in some regard or supplementing the existing flavor impressionto modify its quality, character or taste".

The term "enhance" is used herein to mean the intensification of aflavor or aroma characteristic or note without the modification of thequality thereof. Thus, "enhancement" of a flavor or aroma means that theenhancement agent does not add additional flavor notes.

As used herein, the term "foodstuff" includes both solid and liquidingestible materials which usually do, but need not, have nutritionalvalue. Thus, foodstuffs include soups, convenience foods, beverages,dairy products, candies, vegetables, cereals, soft drinks, snacks andthe like.

As used herein, the term "medicinal product" includes both solids andliquids which are ingestible non-toxic materials which have medicinalvalue such as cough syrups, cough drops, aspirin and chewable medicinaltablets.

The term "chewing gum" is intended to mean a composition which comprisesa substantially water-insoluble, chewable plastic gum base such aschicle, or substitutes therefor, including jelutong, guttakay, rubber orcertain comestible natural or synthetic resins or waxes. Incorporatedwith the gum base in admixture therewith may be plasticizers ofsoftening agents, e.g., glycerine; and a flavoring composition whichincorporates one or more of the caryophyllene alcohol ordihydrocaryophyllene alcohol isomer mixture of our invention, and inaddition, sweetening agents which may be sugars, including sucrose ordextrose and/or artificial sweeteners such as cyclamates or saccharin.Other optional ingredients may also be present.

Substances suitable for use herein as co-ingredients or flavoringadjuvants are well known in the art for such use, being extensivelydescribed in the relevant literature. It is a requirement that any suchmaterial be "ingestibly" acceptable and thus non-toxic and otherwisenon-deleterious particularly from an organoleptic standpoint whereby theultimate flavor and/or aroma of the consumable material used is notcaused to have unacceptable aroma and taste nuances. Such materials mayin general be characterized as flavoring adjuvants or vehiclescomprising broadly stabilizers, thickeners, surface active agents,conditioners, other flavorants and flavor intensifiers.

Stabilizer compounds include preservatives, e.g., sodium chloride;antitoxidants, e.g., calcium and sodium ascorbate, ascorbic acid,butylated hydroxyanisole (mixture of 2- and3-tertiary-butyl-4-hydroxyanisole), butylated hydroxytoluene(2,6-di-tertiary-butyl-4-methylphenol), propyl gallate and the like andsequestrants, e.g., citric acid.

Thickener compounds include carriers, binders, protective colloids,suspending agents, emulsifiers and the like, e.g., agar agar,carrageenan; cellulose and cellulose derivatives such as carboxymethylcellulose and methyl cellulose; natural and synthetic gums such as gumarabic, gum tragacanth; gelatin, proteinaceous materials; lipids;carbohydrates; starches, pectins, and emulsifiers, e.g., mono- anddiglycerides of fatty acids, skim milk powder, hexoses, pentoses,disaccharides, e.g., sucrose corn syrup and the like.

Surface active agents include emulsifying agents, e.g., fatty acids suchas capric acid, caprylic acid, palmitic acid, myristic acid and thelike, mono- and diglycerides of fatty acids, lecithin, defoaming andflavor-dispersing agents such as sorbitan monostearate, potassiumstearate, hydrogenated tallow alcohol and the like.

Conditioners include compounds such as bleaching and maturing agents,e.g., benzoyl peroxide, calcium peroxide, hydrogen peroxide and thelike; starch modifiers such as peracetic acid, sodium chlorite, sodiumhypochlorite, propylene oxide, succinic anhydride and the like, buffersand neutralizing agents, e.g., sodium acetate, ammonium bicarbonate,ammonium phosphate, citric acid, lactic acid, vinegar and the like;colorants, e.g., carminic acid, cochineal, tumeric and curcuma and thelike; firming agents such as aluminum sodium sulfate, calcium chlorideand calcium gluconate; texturizers, anti-caking agents, e.g., aluminumcalcium sulfate and tribasic calcium phosphate; enzymes; yeast foods,e.g., calcium lactate and calcium sulfate; nutrient supplements, e.g.,iron salts such as ferric phosphate, ferrous gluconate and the like,riboflavin, vitamins, zinc sources such as zinc chloride, zinc sulfateand the like.

Other flavorants and flavor intensifiers include aldehydes, esters,natural oils, alcohols, sulfides, ketones, lactones, carboxylic acidsand hydrocarbons such as heliotropin, terpinenol-4, benzaldehyde,anisaldehyde, phenyl acetaldehyde, benzyl formate, benzyl acetate,cis-3-hexenyl benzoate, methyl hexanoate, hexanal, eucalyptol, eugenol,acetaldehyde, ethyl acetate, ethyl butyrate, turpentine gum oil,limonene, gum camphor, isobornyl acetate, borneol, cinnamic aldehyde,cuminic aldehyde, furfural, methyl cinnamate, cassia oil, vanillin,maltol, parahydroxybenzyl acetone, dimethyl sulfide, alpha-ionone,acetic acid, isobutyl acetate, acetone, butyric acid, formic acid,valeric acid, amyl acetate, amyl butyrate, anethol, benzyl salicylate,diacetyl, dimethyl anthranilate, ethyl methylphenylglycidate, ethylsuccinate, ethyl valerate, geraniol, cis-3-hexen-1-ol, 2-hexenylacetate, 2-hexenyl butyrate, hexyl butyrate,4-(p-hydroxyphenyl)-2-butanone, beta-ionone, isobutyl cinnamate,jasmine, lemon essential oil, methyl butyrate, methyl caproate, methyldisulfide, methylp-naphthyl ketone, orris butter, rose absolute,terpinyl acetate, gamma-undecalactone, vanilla and alcohol.

The specific flavoring adjuvant selected for use may be either solid orliquid depending upon the desired physical form of the ultimate product,i.e., foodstuff, whether simulated or natural, and should, in any event,(i) be organoleptically compatible with the caryophyllenealcohol ordihydrocaryophyllene alcohol isomer mixture of our invention by notcovering or spoiling the organoleptic properties (aroma and/or taste)thereof; (ii) be nonreactive with the caryophyllene alcohol ordihydrocaryophyllene alcohol isomer mixture of our invention and (iii)be capable of providing an environment in which the caryophyllenealcohol or dihydrocaryophyllene alcohol isomer mixture of our inventioncan be dispersed or admixed to provide a homogeneous medium. Inaddition, selection of one or more flavoring adjuvants, as well as thequantities thereof will depend upon the precise organoleptic characterdesired in the finished product. Thus, in the case of flavoringcompositions, ingredient selection will vary in accordance with thefoodstuff, chewing gum, medicinal product or toothpaste to which theflavor and/or aroma are to be imparted, modified, altered or enhanced.In contradistinction, in the preparation of solid products, e.g.,simulated foodstuffs, ingredients capable of providing normally solidcompositions should be selected such as verious cellulose derivatives.

As will be appreciated by those skilled in the art, the amount ofcaryophyllene alcohol or dihydrocaryophyllene alcohol isomer mixture ofour invention employed in a particular instance can vary over arelatively wide range, depending upon the desired organoleptic effectsto be achieved. Thus, correspondingly, greater amounts would benecessary in those instances wherein the ultimate food composition to beflavored is relatively bland to the taste, whereas, relatively minorquantities may suffice for purposes of enhancing the composition merelydeficient in natural flavor or aroma. The primary requirement is thatthe amount selected to be effective, i.e., sufficient to alter, modifyor enhance the organoleptic characteristics of the parent composition,whether foodstuff per se, chewing gum, per se, medicinal product per se,toothpaste per se, or flavoring composition.

The use of insufficient quantities of caryophyllene alcohol ordihydrocaryophyllene alcohol isomer mixture of our invention will, ofcourse, substantially vitiate any possibility of obtaining the desiredresults while excess quantities prove needlessly costly and, in extremecases, may disrupt the flavor-aroma balance, thus provingself-defeating. Accordingly, the terminology "effective amount" and"sufficient amount" is to be accorded a significance in the context ofthe present invention consistent with the obtention of desired flavoringeffects.

Thus, and with respect to ultimate food compositions, chewing gumcompositions, medicinal product compositions and toothpastecompositions, it is found that quantities of caryophyllene alcohol ordihydrocaryophyllene alcohol isomer mixture of our invention rangingfrom a small but effective amount, e.g., 0.5 parts per million up toabout 500 parts per million based on total composition are suitable.Concentrations in excess of the maximum quantity stated are not normallyrecommended, since they fail to provide commensurate enhancement oforganoleptic properties. In those instances, wherein the caryophyllenealcohol or dihydrocaryophyllene alcohol isomer mixture of our inventionare added to the foodstuff as an integral component of a flavoringcomposition, it is, of course, essential that the total quantity offlavoring composition employed be sufficient to yield an effectivecaryophyllene derivative concentration in the foodstuff product.

Food flavoring compositions prepared in accordance with the presentinvention preferably contain the caryophyllene alcohol ordihydrocaryophyllene alcohol isomer mixture of our invention inconcentrations ranging from about 0.1% up to about 15% by weight basedon the total weight of the said flavoring composition.

The composition described herein can be prepared according toconventional techniques well known as typified by cake batters and fruitdrinks and can be formulated by merely admixing the involved ingredientswithin the proportions stated in a suitable blender to obtain thedesired consistency, homogeneity of dispersion, etc. Alternatively,flavoring compositions in the form of particulate solids can beconveniently prepared by mixing the caryophyllene alcohol ordihydrocaryophyllene alcohol isomer mixture of our invention with, forexample, gum arabic, gum tragacanth, carrageenan and the like, andthereafter spray-drying the resultant mixture whereby to obtain theparticular solid product. Pre-prepared flavor mixes in powder form,e.g., a fruit-flavored powder mix are obtained by mixing the dried solidcomponents, e.g., starch, sugar and the like and caryophyllenederivatives in a dry blender until the requisite degree of uniformity isachieved.

It is presently preferred to combine with the caryophyllene alcohol ordihydrocaryophyllene alcohol isomer mixture of our invention, thefollowing adjuvants:

Heliotropin;

Terpinenol-4;

Benzaldehyde;

Anisaldehyde;

Phenyl acetaldehyde;

Benzyl formate;

Benzyl acetate;

Cis-3-hexenyl benzoate;

Methyl hexanoate;

Hexanal;

Eucalyptol;

Eugenol;

Acetaldehyde;

Ethyl acetate;

Ethyl butyrate;

Turpentine gum oil;

Limonene;

Gum camphor;

Isobornyl acetate;

Borneol;

Cinnamic aldehyde;

Cuminic aldehyde;

Furfural;

Methyl cinnamate;

Cassia oil;

Vanillin;

Maltol;

Parahydroxybenzylacetone;

Dimethyl sulfide;

Alpha-ionone;

Acetic acid;

Isobutyl acetate;

Acetone;

Butyric acid;

Formic acid;

Valeric acid;

Amyl acetate;

Amyl butyrate;

Anethol;

Benzyl salicylate;

Diacetyl;

Dimethyl anthranilate;

Ethyl methylphenylglycidate;

Ethyl succinate;

Ethyl valerate;

Geraniol;

Cis-3-hexen-1-ol;

2-Hexenyl acetate;

2-Hexenyl butyrate;

Hexyl butyrate;

4-(p-Hydroxyphenyl)-2-butanone;

Beta-ionone;

Isobutyl cinnamate;

Jasmine;

Lemon essential oil;

Methyl butyrate;

Methyl capronate;

Methyl disulfide;

Methyl p-naphthyl ketone;

Orris butter;

Rose absolute;

Terpinyl acetate;

Gamma-undecalactone;

Vanilla; and

Alcohol.

An additional aspect of our invention provides an organolepticallyimproved smoking tobacco product and additives therefor, as well asmethods of making the same which overcome problems heretoforeencountered in which specific desired woody, cigar-box-like and orientaltobacco-like flavor characteristics of natural "Turkish" tobacco (priorto smoking and, on smoking, in the mainstream and in the sidestream) arecreated or enhanced or modified or augmented and may be readilycontrolled and maintained at the desired uniform level regardless ofvariations in the tobacco components of the blend.

This invention further provides improved tobacco additives and methodswhereby various desirable natural turkish type tobacco flavoringcharacteristics with woody, cigar-box and oriental notes may be impartedto smoking tobacco products and may be readily varied and controlled toproduce the desired uniform flavoring characteristics.

In carrying out this aspect of our invention, we add to smoking tobaccomaterials or a suitable substitute therefor (e.g., dried lettuce leaves)an aroma and flavor additive containing as an active ingredient one ormore caryophyllene alcohol or dihydrocaryophyllene alcohol isomermixture of our invention.

In addition to the caryophyllene alcohol dihydrocaryophyllene alcoholisomer mixture of our invention other flavoring aroma additives may beadded to the smoking tobacco material or substitute therefor eitherseparately or in mixture with the caryophyllene alcohol ordihydrocaryophyllene alcohol isomer mixture of our invention as follows:

I. Synthetic Materials:

Beta-ethyl-cinnamaldehyde;

Eugenol;

Dipentene;

Damascenone;

Maltol;

Ethyl maltol;

Delta undecalactone;

Delta decalactone;

Benzaldehyde;

Amyl acetate;

Ethyl butyrate;

Ethyl valerate;

Ethyl acetate;

2-Hexenol-1;

2-Methyl-5-isopropyl-1,3-nonadiene-8-one;

2,6-Dimethyl-2,6-undecadiene-10-one;

2-Methyl-5-isopropylacetophenone;

2-Hydroxy-2,5,5,8a-tetramethyl-1-(2-hydroxyethyl)decahydronaphthalene;

Dodecahydro-3a,6,6,9a-tetramethyl-naphtho-(2,1-b)-furan

4-Hydroxyhexanoic acid, gamma lactone; and

Polyisoprenoid hydrocarbons defined in Example V of U.S. Pat. No.3,589,372 issued on June 29, 1971.

II. Natural Oils:

Celery seed Oil;

Coffee extract;

Bergamot Oil;

Cocoa extract;

Nutmeg Oil; and

Origanum Oil.

An aroma and flavoring concentrate containing one or more caryophyllenealcohol or dihydrocaryophyllene alcohol isomer mixture of our inventionand, if desired, one or more of the above indicated additional flavoringadditives may be added to the smoking tobacco material, to the filter orto the leaf or paper wrapper. The smoking tobacco material may beshredded, cured, cased and blended tobacco material or reconstitutedtobacco material substitutes (e.g., lettuce leaves) or mixtures thereof.The proportions of flavoring additives may be varied in accordance withtaste but insofar as enhancement or the imparting of woody notes, and/orcigar box-like notes and/or oriental notes, we have found thatsatisfactory results are obtained if the proportion by weight of the sumtotal of caryophyllene alcohol or dihydrocaryophyllene alcohol isomermixture of our invention to smoking tobacco material is between 50 ppmand 1,500 ppm (0.015%-0.15%). We have further found that satisfactoryresults are obtained if the proportion by weight of the sum total ofcaryophyllene alcohol or dihydrocaryophyllene alcohol isomer mixture ofour invention used to flavoring material is between 1,500 and 15,000 ppm(0.15% -1.5%).

Any convenient method for incorporating the caryophyllene alcohol ordihydrocaryophyllene alcohol isomer mixture of our invention into thetobacco product may be employed. Thus, the caryophyllene alcohol ordihydrocaryophyllene alcohol isomer mixture of our invention taken aloneor along with other flavoring additives may be dissolved in a suitablesolvent such as ethanol, diethyl ether and/or volatile organic solventsand the resulting solution may either be spread on the cured, cased andblended tobacco material or the tobacco material may be dipped into suchsolution. Under certain circumstances, a solution of the caryophyllenealcohol or dihydrocaryophyllene alcohol isomer mixture of our inventiontaken alone or taken further together with other flavoring additives setforth above, may be applied by means of a suitable applicator such as abrush or roller on the paper or leaf wrapper for the smoking product, orit may be applied to the filter by either spraying, or dipping, orcoating.

Furthermore, it will be apparent that only a portion of the tobacco orsubstitute therefor need be treated and the thus treated tobacco may beblended with other tobaccos before the ultimate tobacco product isformed. In such cases, the tobacco treated may have the caryophyllenealcohol or dihydrocaryophyllene alcohol isomer mixture of our inventionin excess of the amounts of concentrations above indicated so that whenblended with other tobaccos, the final product will have the percentagewithin the indicated range.

In accordance with one specific example of our invention, an aged, curedand shredded domestic burley tobacco is sprayed with a 20% ethyl alcoholsolution of dihydrocaryophyllene alcohol mixture including compoundshaving the structure: ##STR15## in an amount to provide a tobaccocomposition containing 800 ppm by weight of dihydrocaryophyllene alcoholmixture (produced according to Example II) on a dry basis. Thereafter,the ethyl alcohol is removed by evaporation and the tobacco ismanufactured into cigarettes by the usual techniques. The cigarette whentreated as indicated has a desired and pleasing aroma which isdetectable in the main and sidestreams when the cigarette is smoked.This aroma is described as being woody and oriental with a cigar boxnuance.

While our invention is particularly useful in the manufacture of smokingtobacco, such as cigarette tobacco, cigar tobacco and pipe tobacco,other tobacco products, formed from sheeted tobacco dust or fines mayalso be used. Likewise, the caryophyllene alcohol ordihydrocaryophyllene alcohol isomer mixture of our invention can beincorporated with materials such as filter tip materials (e.g.,cellulose acetate filters wherein woody oriental and cigar box-likeeffects are desired), seam paste, packaging materials and the like whichare used along with tobacco to form a product adapted for smoking.Furthermore, the caryophyllene alcohol or dihydrocaryophyllene alcoholisomer mixture can be added to certain tobacco substitutes of natural orsynthetic origin (e.g., dried lettuce leaves) and, accordingly, by theterm "tobacco" as used throughout this specification is meant anycomposition intended for human consumption by smoking or otherwise,whether composed of tobacco plant parts or substitute materials or both.

The caryophyllene alcohol or dihydrocaryophyllene alcohol isomer mixtureand one or more auxiliary perfume ingredients, including, for example,hydrocarbons, alcohols other than those having structures of thedihydrocaryophyllene alcohols and caryophyllene alcohols or ourinvention, ketones, aldehydes, nitriles, esters, lactones or cyclicesters, synthetic essential oils and natural essential oils, may beadmixed so that the combined odors of the individual components producea pleasant and desired fragrance, particularly and preferably in sweet,woody, and peppery fragrances. Such perfume compositions usuallycontains (a) the main note or the "bouquet" or foundation stone of thecomposition; (b) modifiers which round off and accompany the main note;(c) fixatives which include odorous substances which lend a particularnote to the perfume throughout all stages of evaporation and substanceswhich retard evaporation; and (d) topnotes which are usually low boilingfresh smelling materials.

In perfume compositions, it is the individual components whichcontribute to their particular olfactory characteristics, however theover-all sensory effect of the perfume composition will be at least thesum total of the effects of each of the ingredients. Thus, one or moreof the caryophyllene alcohol or dihydrocaryophyllene alcohol isomermixture of our invention can be used to alter, modify or enhance thearoma characteristics of a perfume composition, for example, byutilizing or moderating the olfactory reaction contributed by anotheringredient in the composition.

The amount of caryophyllene alcohol or dihydrocaryophyllene alcoholisomer mixture of our invention which will be effective in perfumecompositions as well as in perfumed articles and colognes depends onmany factors, including the other ingredients, their amounts and theeffects which are desired. It has been found that perfume compositionscontaining as little as 0.01% of caryophyllene alcohol ordihydrocaryophyllene alcohol isomer mixture or even less (e.g., 0.005%)can be used to impart a sweet, woody, peppery odor with borneol-likenuances to soaps, cosmetics, detergents (including anionic, non-ionicand cationic detergents), solid or liquid fabric softeners (e.g.,"BOUNCE®" a registered trademark of the Proctor and Gamble Company ofCincinnati, Ohio), laundry dryer brighteners or other products. Theamount employed can range up to 70% of the fragrance components and willdepend on considerations of cost, nature of the end product, the effectdesired on the finished product and the particular fragrance sought.

The caryophyllene alcohol or dihydrocaryophyllene alcohol isomer mixtureof our invention are useful (taken alone or together with otheringredients in perfume compositions) in detergents and soaps, spaceodorants and deodorants, laundry dryer brighteners, solid or liquidfabric softeners, perfumes, colognes, toilet water, bath preparations,such as lacquers, brilliantines, pomades and shampoos; cosmeticpreparations, such as creams, deodorants, hand lotions and sun screens;powders, such as talcs, dusting powders, face powders and the like. Aslittle as 1% of caryophyllene alcohol or dihydrocaryophyllene alcoholisomer mixture will suffice to impart an intense piney note to woodyperfume formulations. Generally, no more than 3% of caryophyllenealcohol or dihydrocaryophyllene alcohol isomer mixture based on theultimate end product, is required in the perfume composition.

In addition, the perfume composition or fragrance composition of ourinvention can contain a vehicle, or carrier for the caryophyllenealcohol or dihydrocaryophyllene alcohol isomer mixture. The vehicle canbe a liquid such as a non-toxic alcohol, a non-toxic glycol, or thelike. The carrier can also be an absorbent solid, such as a gum (e.g.gum arabic), or components for encapsulating the composition as bycoacervation (such as gelatin).

It will thus be apparent that the caryophyllene alcohol ordihydrocaryophyllene alcohol isomer mixture of our invention can beutilized to alter, modify or enhance sensory properties, particularlyorganoleptic properties, such as flavor(s) and/or fragrance(s) of a widevariety of consumable materials.

The following examples serve to illustrate specific embodiments of ourinvention.

It will be understood that these Examples are illustrative and theinvention is to be considered restricted thereto only as indicated inthe appended claims.

All parts and percentages given herein are by weight unless otherwisespecified.

EXAMPLE I PREPARATION OF CARYOPHYLLENE ALCOHOL ISOMER MIXTURES REACTION

    ______________________________________                                         ##STR16##                                                                     ##STR17##                                                                     ##STR18##                                                                    ______________________________________                                        CHEMICALS:                                                                    caryophyllene oxide    102 g(.46M)                                            aluminum isopropoxide   10.2 g(.05M)                                          toluene                100 cc                                                 sulfuric acid(10%)     100 cc                                                 methylene chloride     100 cc                                                 sodium carbonate        10 g                                                  sodium sulfate          10 g                                                  EQUIPMENT:                                                                    500 ml 3-neck reaction flask                                                  Friedrichs condenser                                                          mechanical stirrer                                                            thermometer                                                                   heating mantle                                                                ______________________________________                                    

PROCEDURE

Caryophyllene oxide, aluminum iosopropoxide, and toluene are charged toa 500 ml three-neck flask equipped with a thermometer, mechanicalstirrer and Friedrichs condenser. The mixture is heated to reflux (111°C.) with stirring for a period of 2.5 hours. After cooling to roomtemperature, 100 cc of cold 10% aqueous sulfuric acid are added, and thereaction mass is stirred for a period of 15 minutes. The resultingorganic phase is separated, and the aqueous phase is extracted with two50 cc portions of methylene chloride. The combined organic phases arewashed with water, saturated aqueous sodium carbonate (approximately 100cc), and then water again until neutral. After drying over anhydroussodium sulfate, the toluene solvent is removed on a rotary evaporatorunder vacuum.

The resulting product (3 components) is purified by distillation througha 30 cm Vigreux column yielding the following fractions:

                                      TABLE I                                     __________________________________________________________________________    Fraction                                                                           Vapor                                                                             Liquid                                                                             Vacuum                                                          No.  Temp.                                                                             Temp.                                                                              mm Hg                                                                              pk 1                                                                             pk 2                                                                             pk 3                                                                             Total                                                                            Weight(g)                                      __________________________________________________________________________    1     31  51  51               41.5                                           2    115 150  3.2              5.4                                            3    135 146  3.2              7.0                                            4    136 146  3.2  27.7                                                                             43.4                                                                             7.0                                                                              78.1                                                                             10.8                                           5    139 150  3.3  28.9                                                                             54.0                                                                             7.5                                                                              90.4                                                                             2.8                                            6    135 157  3.5  27.2                                                                             58.5                                                                             9.1                                                                              94.8                                                                             8.6                                            7    140 155  3.5  22.9                                                                             62.8                                                                             12.4                                                                             98.1                                                                             5.5                                            8    142 155  2.8  20.4                                                                             57.3                                                                             22.0                                                                             99.7                                                                             25.1                                           9    125 190  2.8   8.3                                                                             59.9                                                                             29.3                                                                             97.5                                                                             1.2                                            __________________________________________________________________________

The yield of product greater than 94.8% pure is 40.4 grams or 39.9%.Fractions 7 and 8 are bulked and evaluated. The GLC profile forfractions 7 and 8 is set forth in FIG. 1. The GLC conditions are: 10ft.×1/8in. 5% carbowax-TPA, column programmed at 100°-190° C. at 6° C.per minute.

The three caryophyllene alcohol isomers are trapped for infrared,nuclear magnetic resonance and mass spectral analyses. Peak 1 isconfirmed as the 10,10-dimethyl-2,6-dimethylenebicyclo[7.2.0]undecan-5-ol. Peaks 2 and 3 are identified as isomers of4,11,11-trimethyl-8-methylene bicyclo[7.2.0]undec-3-en-5-ol.

FIG. 2 is the mass spectrum for peak 1 which is confirmed as a compoundhaving the structure: ##STR19##

FIG. 3 is the nuclear magnetic resonance spectrum for the compound ofpeak 1 having the structure: ##STR20##

FIG. 4 is the infrared spectrum for the compound of peak 1 having thestructure: ##STR21##

FIG. 5 is the mass spectrum for the compound having one of thestructures: ##STR22## of peak 2.

FIG. 6 is the NNR spectrum for one of the compounds: ##STR23## of peak2.

FIG. 7 is the infrared spectrum for one of the compounds: ##STR24## ofpeak 2.

FIG. 8 is the mass spectrum for one of the compounds having thestructures: ##STR25## of peak 3.

FIG. 9 is the NMR spectrum of the compound having one of the structures:##STR26## of peak 3.

FIG. 10 is the infrared spectrum for one of the compounds having one ofthe structures: ##STR27## of peak 3.

Fraction 6 above is evaluated as having a sweet, woody, peppery aromawith sweet, "Vertenex-like" notes and a slight borneol background.Fraction 8 is evaluated from a foodflavor standpoint as having a musky,oriental, sandalwood-like aroma with musky, oriental and sandalwoodflavor characteristics causing it to be useful in raspberry, peach,apricot and blueberry flavors at a concentration of 1 ppm.

EXAMPLE II PREPARATION OF DIHYDROCARYOPHYLLENE ALCOHOL ISOMER MIXTURESREACTION:

    ______________________________________                                         ##STR28##                                                                     ##STR29##                                                                    ______________________________________                                        CHEMICALS:                                                                    Dihydro caryophyllene oxide                                                                          91.2 g (0.41 moles)                                    Aluminum isopropoxide  16.4 g (0.08 moles)                                    Toluene                200 cc                                                 Sulfuric acid(10% aqueous)                                                                           100 cc                                                 Sodium carbonate (saturated, aqueous)                                                                500 cc                                                 Sodium sulfate         20 g                                                   EQUIPMENT:                                                                    500 ml three-neck reaction flask                                              Mechanical Stirrer                                                            Thermometer                                                                   Friedrichs condenser                                                          Heating mantle                                                                ______________________________________                                    

The dihydrocaryophyllene oxide, half (8.2 g) of the aluminumisopropoxide and all the toluene are charged to a 500 ml flask equippedas above. The mixture is heated to reflux with stirring and monitored byuse of GLC on a 10'×1/8" carbowax column at 190° C., isothermal. Afterfour hours at reflux, another 8.2 grams of aluminum isopropoxide isadded and the reaction mixture is refluxed overnight. After cooling toroom temperature, 100 cc of cold 10% aqueous sulfuric acid is added andthe reaction mass is stirred for 15 minutes. The organic phase isseparated and the aqueous phase is extracted with two 50 cc portions oftoluene. The combined organic phases are washed with water, thensaturated sodium carbonate and finally water until neutral. Afterdrying, the toluene is removed on a rotary evaporator under vacuum. Theproducts are purified by rushover distillation on a 7 cm Vigreux column.Twelve fractions are collected. Fractions 1-5 contain a good amount ofstarting material. Fractions 6, 7, 8 and 9 and 10 contain product havingaroma quality useful for imparting aromas to perfume compositions,perfumed articles and imparting flavor and fragrance nuances to smokingtobacco and foodstuff flavorants. Fractions 6, 7, 8 and 10 are eachsubjected to GLC separation yielding the following results:

    ______________________________________                                        Fraction                                                                      No.     Peak 1   Peak 2   Peak 3 Peak 4 Total                                 ______________________________________                                        6       13.4     16.7     37.5    9.8   77.4                                  7       13.8     17.8     42.1   15.2   88.9                                  8       12.8     17.4     49.0   18.0   97.2                                  10      10.6     15.1     54.7   14.1   94.5                                  ______________________________________                                    

Fraction 8 is subjected to GLC and the GLC profile is set forth in FIG.11. The infrared spectrum for fraction 8 is set forth in FIG. 12.

EXAMPLE III PERFUMED SOAP

Soap bars are made up containing 100 grams each of soap chips producedaccording to the process of Canadian Pat. No. 1,027,718 ("Process toManufacture Marbled and Striped Soap") quantities of 0.5 grams, 1 gram,1.5 grams, 2.0 grams, 2.5 grams, 3.0 grams, 3.5 grams, 4.0 grams of thecaryophyllene alcohol mixture produced according to Example I (fraction6) are intimately admixed with said soap chips and the resulting slurryis heated to 150° C. using high pressure steam whereupon the resultingmelts is then molded into soap cakes. Each of the soap cakes is thencooled. Each of the soap cakes manifests an excellent sweet, woody,peppery aroma with sweet borneol type undertones.

EXAMPLE IV PERFUMED DETERGENT

Perfumed detergent prepared according to run no. 9 of United KingdomPat. No. 1,495,144 containing linear dodecyl benzene sulfonate (sodiumsalt), sodium silicate and carboxymethyl cellulose optical brightener isintimately admixed at the rates of 1%, 1.5%, 2.0%, 2.5% and 3.0% byweight of the caryophyllene alcohol mixture produced according toExample I, fraction 6. After mixing, the resulting detergent manifestsan excellent stable (to heat and to light) aroma which can be describedas sweet, woody and peppery with a borneol undertone.

EXAMPLE V BLUEBERRY FLAVOR FORMULATION

The following formulation is prepared:

    ______________________________________                                        Ingredients            Parts by Weight                                        ______________________________________                                        Heliotropin            3.0                                                    Terpinenol-4 (10% in 95% aqueous                                               food grade ethanol)   0.2                                                    Benzaldehyde           1.5                                                    Anisaldehyde           0.2                                                    Phenyl acetaldehyde    0.4                                                    Benzyl formate         0.5                                                    Benzyl acetate         2.0                                                    Cis-3-hexenyl benzoate (10% in 95%                                             aqueous food grade ethanol)                                                                         0.5                                                    Methyl hexanoate       2.0                                                    Hexanal                1.0                                                    Eucalyptol (1% in 95% aqueous                                                  food grade ethanol)   0.5                                                    Eugenol                0.2                                                    Acetaldehyde           3.0                                                    Ethyl acetate          21.0                                                   Ethyl butyrate         26.0                                                   Propylene glycol       38.0                                                                          100.0                                                  ______________________________________                                    

The above formulation is split into 3 portions. To the first portion isadded, at the rate of 1%, the caryophyllene alcohol mixture of Example I(bulked fractions 7 and 8). To the second portion is added thedihydrocaryophyllene alcohol mixture produced according to Example II(bulked fractions 6, 7, 8 and 10). The third portion contains nothingadded thereto. The formulations with and without the said caryophyllenealcohol mixture and dihydrocaryophyllene alcohol mixture are eachseparately combined with water at the rate of 100 parts per million. Theflavor with the caryophyllene alcohol mixture and thedihydrocaryophyllene alcohol mixture prepared according to Examples Iand II respectively have more oriental, sandalwood and muskycharacteristics and is closely similar to the flavor of wildblueberries. They are therefor preferred to the basic blueberryformulation which does not contain either of the dihydrocaryophyllenealcohol mixtures or the caryophyllene alcohol mixtures producedaccording to Examples I and II.

EXAMPLE VI RASPBERRY FLAVOR FORMULATION

The following basic raspberry formulation is prepared:

    ______________________________________                                        Ingredients             Parts by Weight                                       ______________________________________                                        Vanillin                2                                                     Maltol                  4                                                     Parahydroxy benzyl acetone                                                                            5                                                     Dimethyl sulfide        1                                                     Alpha-ionone (10% in propylene glycol)                                                                2                                                     Ethyl butyrate          6                                                     Ethyl acetate           16                                                    Isobutyl acetate        14                                                    Acetic acid             10                                                    Acetaldehyde            10                                                    Propylene glycol        930                                                                           1000                                                  ______________________________________                                    

The above formulation is split into three parts. To the first part, atthe rate of 0.3% is added the caryophyllene alcohol mixture producedaccording to Example I (bulked fractions 7 and 8). To the second part isadded at the rate of 0.3% the dihydrocaryophyllene alcohol mixtureproduced according to Example II (bulked fractions 6, 7, 8 and 10). Noadditive is added to the third part. The three formulations are comparedin water at the rate of 50 ppm. The flavors containing the caryophyllenealcohol mixture and the dihydrocaryophyllene alcohol mixture have a moreripe raspberry taste and a woody, raspberry kernel character. Therefore,the raspberry formulations containing the caryophyllene alcohol mixtureand the dihydrocaryophyllene alcohol mixture have more natural like andmore characteristic raspberry flavors and are therefor preferred.

EXAMPLE VII PREPARATION OF A COSMETIC POWDER COMPOSITION

A cosmetic powder is prepared by mixing in a ball mill, 100 g of talcumpowder with 0.25 g of the dihydrocaryophyllene alcohol mixture (bulkedfractions 6, 7, 8 and 10) prepared according to Example II. It has anexcellent sweet, woody and peppery aroma characteristic withborneol-like undertones.

EXAMPLE VIII PERFUMED LIQUID DETERGENT

Concentrated liquid detergents (lysine salt of n-dodecyl benzenesulfonic acid as more specifically described in U.S. Pat. No. 3,948,818,issued on Apr. 6, 1976) with intense sweet, woody and peppery aromas andborneol-like undertones are prepared containing 0.10%, 0.15% and 0.20%of the dihydrocaryophyllene alcohol mixture produced according toExample II (bulked fractions 6, 7, 8 and 10). The detergents areprepared by adding and homogeneously mixing the appropriate quantity ofdihydrocaryophyllene alcohol mixture of Example II. The detergents allpossess intense sweet, woody and peppery aromas, the intensityincreasing with the greater concentration of the product producedaccording to Example II.

EXAMPLE IX PREPARATION OF A COLOGNE AND HANDKERCHIEF PERFUME

The caryophyllene alcohol mixture (bulked fractions 7 and 8) producedaccording to Example I is incorporated into a cologne at a concentrationof 2.5% in 85% aqueous ethanol. A distinct and definite sweet, woody andpeppery aroma with undertones is imparted to the cologne. Thecaryophyllene alcohol mixture of Example I is also added to ahandkerchief perfume at a concentration of 20% (in 95% aqueous ethanol)and a distinct and definite sweet, woody and peppery aroma is impartedto the handkerchief perfume.

EXAMPLE X TOBACCO FILTER

Into a 20 mm cellulose filter is added the caryophyllene alcoholreaction product of Example I (bulked fractions 7 and 8) at the rate of1,000 ppm (10 microliter of a 10% solution of said caryophyllene alcoholmixture is added to the filter). The filter is then attached to a fullflavor cigarette on the market, e.g. (1) Marlboro®, (2) Winston® or (3)Viceroy®, as well as on a Kentucky 1A3 reference cigarette (produced bythe University of Kentucky), yielding the following results:

1. Both cigarettes containing said caryophyllene alcohol mixture, whencompared to a cigarette having a filter without said caryophyllenealcohol mixture give rise to woody, cigar box-like and oriental aromason smoking with a rather noticeable reduced harshness.

2. Both cigarettes containing said caryophyllene alcohol mixture have alesser degree of "hotness" and give rise to a more "Turkish" orientaltaste on smoking.

EXAMPLE XI PERFUME USE OF CARYOPHYLLENE ALCOHOL MIXTURE

The value of the caryophyllene alcohol mixture prepared according toExample I (bulked fractions 7 and 8) may be demonstrated in thefollowing fragrance wherein it is used as a level of 5% by weight:

    ______________________________________                                                       A     B       C       D                                        ______________________________________                                        Linalool         70      70      70    70                                     Linalyl acetate  20      20      20    20                                     Benzyl acetate   20      20      20    20                                     Citronellol      10      10      10    10                                     Geraniol         60      60      10    10                                     Phenyl ethyl alcohol                                                                           110     110     60    60                                     Hydroxy citronellal                                                                            40      40      40    40                                     Cedryl acetate   170     170     100   100                                    Eugenol          20      20      40    40                                     Sandelwood oil   40      40      40    40                                     Diethyl phthalate                                                                              72      122     75    325                                    Hexyl cinnamic aldehyde                                                                        10      10      10    10                                     Coumarin         20      20      40    40                                     Musk xylol       40      40      40    40                                     Musk ambrette    50      50      50    50                                     Bergamot oil     13      13      20    20                                     Ethyl vanillin   4       4       4     4                                      Phenyl ethyl acetate                                                                           10      10      10    10                                     Amyl salicylate  21      21      21    21                                     Benzyl salicylate                                                                              100     100     20    20                                     Patchouli oil    50      50      50    50                                     Caryophyllene alcohol                                                                          50      --      250   --                                     mixture produced according                                                    to Example I (bulked                                                          fractions 7 and 8)                                                                             1000    1000    1000  1000                                   ______________________________________                                    

The addition of 5% caryophyllene alcohol to the above fragrance (A) gavea sweet, woody slightly peppery effect which was much more desirablethan the fragrance without the caryophyllene alcohol. In particular, thedryout notes were considered much more natural.

Very interesting and valuable effects may be obtained by incorporatingcaryophyllene alcohol into the above formulation (C) at 25% by weight.At higher concentrations the caryophyllene alcohol contributes a moremasculine and slightly more floral effect to the fragrance and ispreferred over the fragrance without the caryophyllene alcohol mixtureproduced according to Example I (bulked fractions 7 and 8) (D).

What is claimed is:
 1. The process for rearranging a caryophyllenederivative selected from the group consisting of caryophyllene oxide anddihydro caryophyllene oxide using an aluminum isopropylate catalyst anda toluene solvent comprising the steps of (i) intimately admixingaluminum isopropylate, toluene and the caryophyllene derivative to forma mixture; (ii) heating the resulting mixture at a temperature of from100° C. up to 150° C. for a period of time of from about 1 up to about 5hours; and (iii) recovering the rearranged caryophyllene oxide ordihydro caryophyllene oxide, a mixture of alcohols, from the reactionmass; the concentration of aluminum isopropylate catalyst in thereaction mass varying from about 0.025 molar up to about 0.75 molar; andthe concentration of caryophyllene oxide or dihydro caryophyllene oxidein the reaction mass varying from about 0.25 molar up to about 1.00molar.
 2. The process of claim 1 wherein a mixture of caryophyllenealcohols is prepared, said process comprising the step of intimatelyadmixing caryophyllene oxide with an aluminum isopropylate catalyst andtoluene and heating the resulting mixture at a temperature of from 100°C. up to 150° C. for a period of time of from 1 up to 5 hours yielding aproduct consisting essentially of compounds having the structures:##STR30##
 3. The process of claim 1 wherein the reaction temperaturerange is reflux temperature at atmospheric pressure, from 110° up to112° C.
 4. The process of claim 3 wherein the concentration ofcaryophyllene oxide or dihydro caryophyllene oxide in the reaction massis from 0.40 up to 0.50 molar.
 5. The process of claim 4 wherein theconcentration of aluminum isopropylate in the reaction mass is fromabout 0.04-0.10 molar.